EP0810269A2 - Transparent bismuth vanadate pigments - Google Patents
Transparent bismuth vanadate pigments Download PDFInfo
- Publication number
- EP0810269A2 EP0810269A2 EP19970810315 EP97810315A EP0810269A2 EP 0810269 A2 EP0810269 A2 EP 0810269A2 EP 19970810315 EP19970810315 EP 19970810315 EP 97810315 A EP97810315 A EP 97810315A EP 0810269 A2 EP0810269 A2 EP 0810269A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bismuth
- coating
- pigment
- minutes
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 53
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 34
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 28
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000004922 lacquer Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 150000002843 nonmetals Chemical class 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- -1 bismuth vanadates Chemical class 0.000 claims description 9
- 235000021317 phosphate Nutrition 0.000 claims description 9
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 150000004679 hydroxides Chemical class 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- 150000001621 bismuth Chemical class 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 75
- 239000000725 suspension Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 5
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 5
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- LPDWOEAWNMGOAO-UHFFFAOYSA-N (4,7,8-trimethylquinolin-2-yl)hydrazine Chemical compound CC1=CC(NN)=NC2=C(C)C(C)=CC=C21 LPDWOEAWNMGOAO-UHFFFAOYSA-N 0.000 description 1
- ITFDYXKCBZEBDG-UHFFFAOYSA-N 2-(1-methylpyrrol-2-yl)ethanamine Chemical compound CN1C=CC=C1CCN ITFDYXKCBZEBDG-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- RLKZVQFRPREHAD-UHFFFAOYSA-N O.[Sb+]=O Chemical compound O.[Sb+]=O RLKZVQFRPREHAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- IPNGSXQUQIUWKO-UHFFFAOYSA-N bismuth;fluoro hypofluorite Chemical compound [Bi].FOF IPNGSXQUQIUWKO-UHFFFAOYSA-N 0.000 description 1
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 1
- IAQAJTTVJUUIQJ-UHFFFAOYSA-N bismuth;trihydrate Chemical compound O.O.O.[Bi] IAQAJTTVJUUIQJ-UHFFFAOYSA-N 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229940074568 calcium hexafluorosilicate Drugs 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- KKFPIBHAPSRIPB-UHFFFAOYSA-N cerium(3+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Ce+3].[Ce+3] KKFPIBHAPSRIPB-UHFFFAOYSA-N 0.000 description 1
- QIICBUVIQUVXPN-UHFFFAOYSA-N cerium(4+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[Ce+4] QIICBUVIQUVXPN-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- PKSIZOUDEUREFF-UHFFFAOYSA-N cobalt;dihydrate Chemical compound O.O.[Co] PKSIZOUDEUREFF-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- WKLWZEWIYUTZNJ-UHFFFAOYSA-K diacetyloxybismuthanyl acetate Chemical compound [Bi+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WKLWZEWIYUTZNJ-UHFFFAOYSA-K 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- ZIWYFFIJXBGVMZ-UHFFFAOYSA-N dioxotin hydrate Chemical compound O.O=[Sn]=O ZIWYFFIJXBGVMZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- PMQJYWORJJEMQC-UHFFFAOYSA-N manganese;dihydrate Chemical compound O.O.[Mn] PMQJYWORJJEMQC-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920002842 oligophosphate Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- LCLMKSPTPNBUGU-UHFFFAOYSA-N oxotin;hydrate Chemical compound O.[Sn]=O LCLMKSPTPNBUGU-UHFFFAOYSA-N 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JUWHRJSDVJDFJG-UHFFFAOYSA-J vanadium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[V+4] JUWHRJSDVJDFJG-UHFFFAOYSA-J 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0006—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black containing bismuth and vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
Definitions
- the present application relates to transparent bismuth vanadate pigments and their preparation.
- the pigments used to achieve a transparent yellow color in the paint, plastics and printing ink industries are, with the exception of transparent yellow iron oxide, organic pigments.
- the long, e.g. bismuth vanadate pigments known from US Pat. Nos. 3,843,554 and 4,115,142, which are particularly valued for their low toxicity and high color saturation and fastness properties, have hitherto existed only as highly opaque variants. For this reason, the use of bismuth vanadate pigments produced using previously known methods is limited to opaque coloring.
- the acidic bismuth salt solution is an aqueous nitric acid solution of bismuth (III) acetate or preferably Bi (III) nitrate
- the vanadate solution is, for example, a solution of NaVO 3 , NH 4 VO 3 , Na 3 VO 4 or V 2 O 5 in sodium hydroxide solution or potassium hydroxide solution. It is advantageous to thoroughly disperse the pigment precursor during or after the precipitation in the reaction solution, before the coating process (b), in a conventional dispersing apparatus.
- the pigment precursors produced under (a) are preferably pigment precursors which are known as C.I. Pigment Yellow 184 referred to commercially available bismuth vanadate pigments (cf. The Bulletin of the Bismuth Institute 68, 1995).
- the coating according to (b) is preferably carried out with 10 to 30% by weight of coating material, based on the total amount.
- Suitable coating materials are inorganic compounds, e.g.
- Phosphates and pyrophosphates of zinc, aluminum, calcium, magnesium, bismuth, iron or chromium such as, for example, zinc phosphate [Zn 3 (PO 4 ) 2 ], aluminum phosphate [AlPO 4 ], Calcium phosphate [Ca 3 (PO 4 ) 2 ], calcium pyrophosphate [Ca 2 P 2 O 7 ], magnesium phosphate [Mg 3 (PO 4 ) 2 ], bismuth phosphate [BiPO 4 ], iron (II) phosphate [Fe 3 (PO 4 ) 2 ], iron (III) phosphate [FePO 4 ], chromium (III) phosphate [CrPO 4 ], and calcium salts of oligophosphates, such as the calcium salt of Graham's salt, or a mixture of phosphates ;
- Hydroxides such as aluminum hydroxide [Al (OH) 3 ], zinc hydroxide [Zn (OH) 2 ], iron (II) hydroxide [Fe (OH) 2 ], iron (III) hydroxide [Fe (OH) 3 ], Strontium hydroxide [Sr (OH) 2 ], calcium hydroxide [Ca (OH) 2 ], bismuth hydroxide [Bi (OH) 3 ], barium hydroxide [Ba (OH) 2 ], chromium (III) hydroxide [Cr (OH) 3 ], Vanadium (IV) hydroxide [V (OH) 4 ], cobalt (II) hydroxide [Co (OH) 2 ], manganese hydroxide [Mn (OH) 2 ] or a mixture of hydroxides;
- Oxides or water-containing oxides such as tin (II) oxide hydrate [SnO ⁇ xH 2 O], tin (IV) oxide hydrate [SnO 2 • xH 2 O], titanium dioxide hydrate [TiO 2 • xH 2 O], zirconium dioxide hydrate [ZrO 2 • xH 2 O], cerium (III) oxide hydrate [Ce 2 O 3 • XH 2 O], cerium (IV) oxide hydrate [CeO 2 • xH 2 O], silicon dioxide [SiO 2 ], antimony (III) oxide hydrate [Sb 2 O 3 • xH 2 O], antimony (V) oxide hydrate [Sb 2 O 5 • xH 2 O] or a mixture of oxides or water-containing oxides.
- tin (II) oxide hydrate [SnO ⁇ xH 2 O] tin (IV) oxide hydrate [SnO 2 • xH 2 O]
- carbonates, nitrates, fluorides, fluorosilicates, molybdates, tungstates and in particular sulfates such as calcium carbonate [CaCO 3 ], magnesium carbonate [MgCO 3 ], bismuth oxy nitrate [BiO (NO 3 )], bismuth oxy fluoride [BiOF], calcium hexafluorosilicate [CaSiF 6 ], calcium molybdate [CaMoO 4 ], calcium sulfate [CaSO 4 ] or mixtures thereof.
- hydroxides and in particular the phosphates of zinc and aluminum are preferred.
- a mixture of zinc and aluminum phosphate is particularly preferred.
- the coating agent is expediently metered into the pigment precursor suspension in aqueous solution and, if appropriate, by adding an acid or base Dependent pH used used coating material, it being advantageous to thoroughly disperse the resulting product during or after the addition of the coating agent, before the thermal treatment, in a conventional dispersing apparatus, for example a high-pressure homogenizer or a high-speed stirrer.
- Suitable acids are e.g. Phosphoric acid and acetic acid and especially nitric acid.
- Aqueous alkali hydroxide solutions or ammonia solutions, preferably aqueous sodium hydroxide solution, can expediently be used as bases.
- the pH is important for the coating so that the coating materials fail. In the case of phosphates, pH values between 5 and 10, preferably between 5 and 7, are expedient.
- For hydroxides a pH range between 1 (bismuth hydroxide) and 11 (calcium and barium hydroxide) can be used; however, the preferred aluminum and zinc hydroxides are in the range 4 to 8. Most oxides or water-containing oxides are precipitated at pH values between 2 and 4. However, higher pH values up to 10 have no negative influence. Silicon oxide precipitates in a pH range of 2-9, preferably 6-9. The other salts listed fall out in a pH range between 1 (bismuth oxin nitrate) and 8 (calcium molybdate).
- the thermal treatment (c) (calcination) is carried out by conventional methods, preferably between 100 and 600 ° C., particularly preferably between 300 and 450 ° C. and in particular at 400 ° C.
- the coating can, if appropriate for the intended use, be removed by treatment with an acid or base and, if appropriate, replaced with other customary coating agents, without impairing the transparency.
- Suitable acids and bases are e.g. the same ones mentioned above in connection with pH adjustment.
- the products obtained by the process according to the invention are characterized by a transparency never previously achieved with bismuth vanadate pigments. They are therefore new and form a further subject of the present application.
- L * (white) or L * (black) are measured by color measurement of an alkyd-melamine lacquer application with a pigment content (solids content) of 38%, with a layer thickness (dry) of 40 ⁇ m on a black and white contrast cardboard and calculation the ClELAB formula (ISO 7724-1 to 7724-3).
- the present invention accordingly also relates to bismuth vanadate pigments of the general composition Bi 2nd O 3rd x V 2nd O 5 , Bismuth and vanadium can be partially replaced by other metals or non-metals, characterized in that they have a transparency of ⁇ L *> 4 in an alkyd-melamine lacquer application with a pigment content of 38%, with a layer thickness, dry, of 40 ⁇ m .
- the metals and non-metals which can partially replace bismuth and vanadium, are preferably Li, Mg, Zn, Al and in particular Ca, and W and in particular P and Mo.
- Bismuth vanadate pigments based on the C.I. Pigment Yellow 184 types.
- the transparent bismuth vanadates according to the invention can be used as pigments for high-molecular organic materials.
- High molecular weight organic materials which can be pigmented with the bismuth vanadates according to the invention are, for example, cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins and synthetic resins, such as polymerization resins or condensation resins, for example aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polyethylene and polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes, polyesters, rubbers, casein, silicone and silicone resins , individually or in mixtures.
- cellulose ethers and esters such as ethyl cellulose, nitrocellulose, cellulose acetate and cellulose butyrate
- natural resins and synthetic resins such as polymerization resins
- the bismuth vanadate according to the invention can be used in an amount of 0.01 to 75% by weight, preferably 0.1 to 50% by weight.
- the colorations obtained are distinguished, in addition to the extraordinarily high color purity and transparency, by high color strength, good dispersibility, good resistance to overpainting, migration, heat, light and weather, and by a good shine from.
- the bismuth vanadates according to the invention are particularly notable for their high transparency. Accordingly, they are preferably suitable for coloring plastics, printing inks and aqueous and / or solvent-based paints, in particular automotive paints. Their use is particularly preferred for metallic effect coatings (metal or mica).
- Example 1 98.4 g of bismuth nitrate pentahydrate and 6.4 g of calcium nitrate tetrahydrate are dissolved with stirring in 74.4 g of nitric acid (54%) and 580 ml of water.
- the solution obtained is mixed with a vanadate solution consisting of 35.4 g of sodium orthovanadate, 4.0 g of sodium hydroxide and 6.6 g of sodium molybdate dihydrate in 600 ml of water within 3 minutes with vigorous stirring.
- the pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution raised.
- the pH of the suspension is increased to a value of 6.5 within 20 minutes by adding 1 molar sodium hydroxide solution and stirring is continued for a further 30 minutes.
- a solution of 39.0 g of phosphoric acid (75%), 53.0 g of aluminum sulfate hydrate and 44.0 g of zinc sulfate heptahydrate dissolved in 300 ml of water is added to this suspension in 20 minutes, whereupon the pH drops. If the pH falls below 2.0, 20% sodium hydroxide solution is added.
- the pH of the suspension is then adjusted to a value of 6.5 in 1 minute with 1 molar sodium hydroxide solution and stirred for a further 30 minutes.
- the solid obtained is calcined at 400 ° C. for 20 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
- the pigment obtained is applied in an AM lacquer according to the following procedure:
- the paint is drawn out on a contrasting cardboard (wet film thickness 75 ⁇ m), flashed off for 20 minutes and baked at 130 ° C for 30 minutes.
- Example 2 98.4 g of bismuth nitrate pentahydrate and 6.4 g of calcium nitrate tetrahydrate are dissolved with stirring in 74.4 g of nitric acid (54%) and 580 ml of water.
- the solution obtained is mixed with a vanadate solution consisting of 35.4 g of sodium orthovanadate, 4.0 g of sodium hydroxide and 6.6 g of sodium molybdate dihydrate in 600 ml of water within 3 minutes with vigorous stirring.
- the pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution.
- the pH of the suspension is increased to 6.5 within 20 minutes by adding 1 molar sodium hydroxide solution and the mixture is stirred for a further 30 minutes.
- a solution of 9.8 g of phosphoric acid (75%), 13.3 g of aluminum sulfate hydrate and 11.0 g of zinc sulfate heptahydrate dissolved in 300 ml of water is added to this suspension in 5 minutes, after which a pH of 1.2 one poses.
- the pH of the suspension is then adjusted to a value of 6.5 in 1 minute with 1 molar sodium hydroxide solution and stirred for a further 30 minutes.
- the solid obtained is calcined at 400 ° C. for 20 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
- the pigment obtained is applied in an AM lacquer and subjected to a color measurement.
- Example 3 239.0 g bismuth nitrate pentahydrate and 12.8 g calcium nitrate tetrahydrate are dissolved with stirring in 140.0 g nitric acid (54%) and 1150.0 ml water.
- a vanadate solution consisting of 70.8 g of sodium orthovanadate, 7.9 g of sodium hydroxide and 13.2 g of sodium molybdate dihydrate in 700 ml of water is added to the resulting solution within 1 minute with vigorous stirring.
- the pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution.
- the pH of the suspension is increased to a value of 6.5 within 20 minutes by adding 1 molar sodium hydroxide solution and stirring is continued for a further 30 minutes.
- a solution of 39.0 g of phosphoric acid (75%), 53.0 g of aluminum sulfate hydrate and 44.0 g of zinc sulfate heptahydrate dissolved in 200 ml of water is added to this suspension in 5 minutes, after which the pH is 1.0 sets.
- the pH of the suspension is then adjusted to a value of 6.5 in 50 minutes with 50% sodium hydroxide solution and stirred for a further 30 minutes.
- the solid obtained is calcined at 400 ° C. for 16 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
- Example 4 98.4 g of bismuth nitrate pentahydrate and 6.4 g of calcium nitrate tetrahydrate are dissolved with stirring in 74.4 g of nitric acid (54%) and 580 ml of water.
- a vanadate solution consisting of 35.4 g of sodium orthovanadate, 4.0 g of sodium hydroxide and 6.6 g of sodium molybdate dihydrate in 600 ml of water is added to the resulting solution within 3 minutes with vigorous stirring.
- the pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution.
- the pH of the suspension is increased to 6.5 within 60 minutes by adding 20% sodium hydroxide solution and the mixture is left to stir for a further 30 minutes.
- a solution of 53.0 g of aluminum sulfate hydrate and 44.0 g of zinc sulfate heptahydrate dissolved in 600 ml of water is added to this suspension in 10 minutes, after which a pH of 3.1 is established.
- the pH of the suspension is then adjusted to a value of 6.5 in 1 minute with 1 molar sodium hydroxide solution and stirred for a further 30 minutes. After filtration, washing three times with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 24 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
- Example 5 123.6 g of bismuth nitrate pentahydrate are dissolved with stirring in 53.0 g of nitric acid (54%) and 570 ml of water. The solution obtained is mixed with a vanadate solution consisting of 48.9 g of sodium orthovanadate, 5.5 g of sodium hydroxide in 600 ml of water within 3 minutes with vigorous stirring. The pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution. After a stirring time of 30 minutes, the pH of the suspension is increased to 6.5 within 60 minutes by adding 20% sodium hydroxide solution and the mixture is stirred for a further 16 hours.
- the annealing product After the annealing product has cooled, it is deagglomerated in a powder mill. 50 g of the pigment obtained are redispersed in 2.0 l of water and 5.0 g of sodium hexametaphosphate for 20 minutes at 100 ° C. using a high-speed stirrer. A solution of 7.6 g of cerium (III) chloride in 250 ml of water is added to the suspension obtained in 10 minutes, after which a pH of 4.1 is established. The pH of the suspension is raised to a value of 10.0 with 1 molar sodium hydroxide solution in 15 minutes and stirring is continued for 30 minutes. After filtration, washing twice with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 16 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
Abstract
Description
Die vorliegende Anmeldung betrifft transparente Bismuthvanadat-Pigmente und ihre Herstellung.The present application relates to transparent bismuth vanadate pigments and their preparation.
Bei den zur Erzielung eines transparenten gelben Farbtones in der Lack-, Kunststoff- und Druckfarbenindustrie eingesetzten Pigmenten handelt es sich, mit Ausnahme von transparentem gelbem Eisenoxid, um organische Pigmente. Die seit langem, z.B. aus den US-Patenten 3 843 554 und 4 115 142, bekannten Bismuthvanadat-Pigmente, die insbesondere wegen ihrer geringen Toxizität und ihrer hohen Farbsättigung und Echtheitseigenschaften sehr geschätzt werden, existierten bislang nur als hochdeckende Varianten. Deshalb ist der Einsatz der nach bisher bekannten Methoden hergestellten Bismuthvanadat-Pigmenten auf deckende Einfärbungen beschränkt.The pigments used to achieve a transparent yellow color in the paint, plastics and printing ink industries are, with the exception of transparent yellow iron oxide, organic pigments. The long, e.g. bismuth vanadate pigments known from US Pat. Nos. 3,843,554 and 4,115,142, which are particularly valued for their low toxicity and high color saturation and fastness properties, have hitherto existed only as highly opaque variants. For this reason, the use of bismuth vanadate pigments produced using previously known methods is limited to opaque coloring.
Um die obenerwähnten Vorteile der Bismuth vanadat-Pigmente auch für die heutzutage stark aufkommenden transparenten Applikationen zu nützen, war es wünschenswert, diese auch in einer transparenten Variante herstellen zu können.In order to be able to use the above-mentioned advantages of the bismuth vanadate pigments for the transparent applications that are becoming increasingly popular today, it was desirable to be able to produce them in a transparent variant.
Aus der einschlägigen Literatur sind unzählige Herstellungsmethoden für verschieden artige Bismuthvanadat-Pigmente bekannt. Alle führen zu opaken Formen. Im allgemeinen wird durch Vermischen von bismuth- und vanadium haltiger Lösungen in Gegenwart lösliche r Metallsalze und gegebenenfalls löslicher Phosphate, Sulfate und/oder Silikate der amorphe Pigmentvorläufer ausgefällt, der nachträglich durch Calcinieren in die pigmentäre Form überführt wird. Verfahren dieser Art sind z.B. in US 5 536 309, US 4 115 142, US 4 272 296, US 4 316 746, US 4 455 174, US 4 752 460, US 5 203 917, US 5 336 312, US 5 399 197 und EP 441 101 beschrieben.Countless production methods for various types of bismuth vanadate pigments are known from the relevant literature. All lead to opaque shapes. In general, by mixing solutions containing bismuth and vanadium in the presence of soluble metal salts and optionally soluble phosphates, sulfates and / or silicates, the amorphous pigment precursor is precipitated, which is subsequently converted into the pigmentary form by calcination. Methods of this type are e.g. in US 5 536 309, US 4 115 142, US 4 272 296, US 4 316 746, US 4 455 174, US 4 752 460, US 5 203 917, US 5 336 312, US 5 399 197 and EP 441 101 .
Es ist nun gefunden worden, dass durch Beschichtung eines nach üblichen Methoden, wie sie beispielsweise in den eben erwähnten Publikationen beschrieben sind, hergestellten Pigmentvorläufers mit einem für die Beschichtung von Pigmenten üblichen Beschichtungsmaterial und anschliessender Calcinierung, ganz überraschend transparente Bismuthvanadat-Pigmente entstehen, mit ansonsten guten Pigmenteigenschaften.It has now been found that by coating a pigment precursor produced by customary methods, as described, for example, in the publications just mentioned, with a coating material customary for coating pigments and subsequent calcination, surprisingly transparent bismuth vanadate pigments are formed, otherwise good pigment properties.
Die vorliegende Erfindung betrifft demnach ein Verfahren zur Herstellung von transparenten Bismuthvanadat-Pigmenten, dadurch gekennzeichnet, dass
- a) ein amorpher Pigmentvorläufer nach allgemein üblichen Methoden durch Ausfällung aus einer sauren Bismuthsalzlösung und einer Vanadatlösung, welche gelöste Metallsalze, Metalloxide oder Nichtmetalloxide enthalten können, hergestellt wird,
- b) der so erhaltene amorphe Pigmentvorläufer mit 1 bis 50 Gew.%, bezogen auf die Gesamtmenge, eines für die Beschichtung von Pigmenten üblichen anorganischen Beschichtungsmaterials bei einem pH zwischen 1 und 11 überzogen und dann
- c) bei Temperaturen von 50 bis 800°C nach allgemein bekannten Methoden thermisch behandelt und anschliessend desagglomeriert wird.
- a) an amorphous pigment precursor is prepared by precipitation from an acid bismuth salt solution and a vanadate solution, which may contain dissolved metal salts, metal oxides or non-metal oxides, by generally customary methods,
- b) the amorphous pigment precursor thus obtained is coated with 1 to 50% by weight, based on the total amount, of an inorganic coating material customary for the coating of pigments at a pH between 1 and 11 and then
- c) thermally treated at temperatures of 50 to 800 ° C according to generally known methods and then deagglomerated.
Die Möglichkeiten der Herstellung verschiedenartiger amorpher Pigmentvorläufer gemäss (a) ist allgemein bekannt und z.B. in den obenerwähnten Patent publikationen beschrieben. So handelt es sich z.B. bei der sauren Bismuth salzlösung um eine wässrige salpetersaure Lösung von Bismuth(lll)-acetat oder bevorzugt Bi(lll)-nitrat und bei der Vanadat lösung z.B. um eine Lösung von NaVO3, NH4VO3, Na3VO4 oder V2O5 in Natronlauge oder Kalilauge. Es ist von Vorteil den Pigmentvorläufer während oder nach der Fällung in der Reaktions lösung, vor dem Beschichtungsvorgang (b), in einer üblichen Dispergierapparatur gründlich zu dispergieren.The possibilities of producing various amorphous pigment precursors according to (a) are generally known and are described, for example, in the above-mentioned patent publications. For example, the acidic bismuth salt solution is an aqueous nitric acid solution of bismuth (III) acetate or preferably Bi (III) nitrate, and the vanadate solution is, for example, a solution of NaVO 3 , NH 4 VO 3 , Na 3 VO 4 or V 2 O 5 in sodium hydroxide solution or potassium hydroxide solution. It is advantageous to thoroughly disperse the pigment precursor during or after the precipitation in the reaction solution, before the coating process (b), in a conventional dispersing apparatus.
Bei den unter (a) erzeugten Pigment vorläufern handelt es sich vorzugsweise um Pigmentvorläufer der als C.I. Pigment Yellow 184 bezeichneten handelsüblichen Bismuth vanadat-Pigmente (vgl. The Bulletin of the Bismuth Institute 68, 1995).The pigment precursors produced under (a) are preferably pigment precursors which are known as C.I. Pigment Yellow 184 referred to commercially available bismuth vanadate pigments (cf. The Bulletin of the Bismuth Institute 68, 1995).
Die Beschichtung gemäss (b) erfolgt vorzugsweise mit 10 bis 30 Gew.% Beschichtungsmaterial, bezogen auf die Gesamtmenge.The coating according to (b) is preferably carried out with 10 to 30% by weight of coating material, based on the total amount.
Geeignete Beschichtungsmaterialien sind anorganische Verbindungen, wie z.B.Suitable coating materials are inorganic compounds, e.g.
Phosphate und Pyrophosphate von Zink, Aluminium, Calcium, Magnesium, Bismuth, Eisen oder Chrom, wie z.B. Zinkphosphat [Zn3(PO4)2], Aluminiumphosphat [AlPO4], Calciumphosphat [Ca3(PO4)2], Calciumpyrophosphat [Ca2P2O7], Magnesiumphosphat [Mg3(PO4)2], Bismuthphosphat [BiPO4], Eisen(II)-phosphat [Fe3(PO4)2], Eisen(III)-phosphat [FePO4], Chrom(lll)-phosphat [CrPO4], sowie Calcium-Salze von Oligophosphaten, wie z.B. das Calcium-Salz des Graham'schen Salzes, oder eine Mischung von Phosphaten;Phosphates and pyrophosphates of zinc, aluminum, calcium, magnesium, bismuth, iron or chromium, such as, for example, zinc phosphate [Zn 3 (PO 4 ) 2 ], aluminum phosphate [AlPO 4 ], Calcium phosphate [Ca 3 (PO 4 ) 2 ], calcium pyrophosphate [Ca 2 P 2 O 7 ], magnesium phosphate [Mg 3 (PO 4 ) 2 ], bismuth phosphate [BiPO 4 ], iron (II) phosphate [Fe 3 (PO 4 ) 2 ], iron (III) phosphate [FePO 4 ], chromium (III) phosphate [CrPO 4 ], and calcium salts of oligophosphates, such as the calcium salt of Graham's salt, or a mixture of phosphates ;
Hydroxide, wie z.B. Aluminiumhydroxid [Al(OH)3], Zinkhydroxid [Zn(OH)2], Eisen(II)-hydroxid [Fe(OH)2], Eisen(lll)-hydroxid [Fe(OH)3], Strontiumhydroxid [Sr(OH)2], Calciumhydroxid [Ca(OH)2], Bismuthhydroxid [Bi(OH)3], Bariumhydroxid [Ba(OH)2], Chrom(III)-hydroxid [Cr(OH)3], Vanadium(lV)-hydroxid [V(OH)4], Cobalt(ll)-hydroxid [Co(OH)2], Manganhydroxid [Mn(OH)2] oder eine Mischung von Hydroxiden;Hydroxides such as aluminum hydroxide [Al (OH) 3 ], zinc hydroxide [Zn (OH) 2 ], iron (II) hydroxide [Fe (OH) 2 ], iron (III) hydroxide [Fe (OH) 3 ], Strontium hydroxide [Sr (OH) 2 ], calcium hydroxide [Ca (OH) 2 ], bismuth hydroxide [Bi (OH) 3 ], barium hydroxide [Ba (OH) 2 ], chromium (III) hydroxide [Cr (OH) 3 ], Vanadium (IV) hydroxide [V (OH) 4 ], cobalt (II) hydroxide [Co (OH) 2 ], manganese hydroxide [Mn (OH) 2 ] or a mixture of hydroxides;
Oxide oder wasserhaltige Oxide, wie z.B. Zinn(ll)-oxidhydrat [SnO·xH2O], Zinn(IV)-oxidhydrat [SnO2•xH2O], Titandioxidhydrat [TiO2•xH2O], Zirkondioxidhydrat [ZrO2•xH2O], Cer(lll)-oxidhydrat [Ce2O3•XH2O], Cer(lV)-oxidhydrat [CeO2•xH2O], Siliciumdioxid [SiO2], Antimon(III)-oxidhydrat [Sb2O3•xH2O], Antimon(V)-oxidhydrat [Sb2O5•xH2O] oder eine Mischung von Oxiden bzw. wasserhaltigen Oxiden.Oxides or water-containing oxides, such as tin (II) oxide hydrate [SnO · xH 2 O], tin (IV) oxide hydrate [SnO 2 • xH 2 O], titanium dioxide hydrate [TiO 2 • xH 2 O], zirconium dioxide hydrate [ZrO 2 • xH 2 O], cerium (III) oxide hydrate [Ce 2 O 3 • XH 2 O], cerium (IV) oxide hydrate [CeO 2 • xH 2 O], silicon dioxide [SiO 2 ], antimony (III) oxide hydrate [Sb 2 O 3 • xH 2 O], antimony (V) oxide hydrate [Sb 2 O 5 • xH 2 O] or a mixture of oxides or water-containing oxides.
Ebenfalls geeignet sind Carbonate, Nitrate, Fluoride, Fluoro silicate, Molybdate, Wolframate und insbesondere Sulfate, wie z.B. Calciumcarbonat [CaCO 3], Magnesiumcarbonat [MgCO3], Bismuthoxinitrat [BiO(NO3)], Bismuthoxifluorid [BiOF], Calciumhexafluorosilicat [CaSiF6], Calciummolybdat [CaMoO4], Calciumsulfat [CaSO4] oder Mischungen davon.Also suitable are carbonates, nitrates, fluorides, fluorosilicates, molybdates, tungstates and in particular sulfates, such as calcium carbonate [CaCO 3 ], magnesium carbonate [MgCO 3 ], bismuth oxy nitrate [BiO (NO 3 )], bismuth oxy fluoride [BiOF], calcium hexafluorosilicate [CaSiF 6 ], calcium molybdate [CaMoO 4 ], calcium sulfate [CaSO 4 ] or mixtures thereof.
Weiterhin sind alle Kombinationen von Phosphaten, Hydroxiden, Oxiden bzw. wasserhaltigen Oxiden und Salzen möglich, die sich durch Auffällen auf amorphen Pigmentvorläufer aufbringen lassen.Furthermore, all combinations of phosphates, hydroxides, oxides or water-containing oxides and salts are possible, which can be applied to amorphous pigment precursors by precipitation.
Bevorzugt werden die Hydroxyde und insbesondere die Phosphate von Zink und Aluminium. Besonders bevorzugt ist ein Gemisch von Zink- und Aluminium phosphat.The hydroxides and in particular the phosphates of zinc and aluminum are preferred. A mixture of zinc and aluminum phosphate is particularly preferred.
Das Beschichtungsmittel wird zweckmässig in wässriger Lösung der Pigmentvorläufersuspension zudosiert und gegebenenfalls durch Zugabe einer Säure oder Base ein vom verwendetem Beschichtungsmaterial abhängiger pH eingestellt, wobei es vorteilhaft ist, das anfallende Produkt während oder nach der Zugabe des Beschichtungsmittels, vor der thermischen Behandlung, in einer üblichen Dispergierapparatur, z.B. einem Hochdruckhomogenisator oder einem Hochgeschwindigkeits rührer, gründlich zu dispergieren.The coating agent is expediently metered into the pigment precursor suspension in aqueous solution and, if appropriate, by adding an acid or base Dependent pH used used coating material, it being advantageous to thoroughly disperse the resulting product during or after the addition of the coating agent, before the thermal treatment, in a conventional dispersing apparatus, for example a high-pressure homogenizer or a high-speed stirrer.
Geeignete Säuren sind z.B. Phosphorsäure und Essigsäure und insbesondere Salpetersäure. Als Basen können zweckmässig wässrige Alkalihydroxyd lösungen bzw. Ammoniaklösungen verwendet werden, vorzugsweise wässrige Natronlauge. Der pH ist für die Beschichtung wichtig, damit die Beschichtungs materialien ausfallen. Bei Phosphaten sind pH-Werte zwischen 5 und 10, bevorzugt, zwischen 5 und 7 zweckmässig. Bei Hydroxyden ist ein pH-Bereich zwischen 1 (Bismuthhydroxid) und 11 (Calcium- und Bariumhydroxyd) einsetzbar; die bevorzugten Aluminium- und Zinkhydroxyd fallen jedoch im Bereich zwischen 4 und 8 aus. Die meisten Oxide bzw. wasserhaltigen Oxide werden bei pH-Werten zwischen 2 und 4 ausgefällt. Höhere pH-Werte bis zu 10 haben aber keinen negativen Einfluss. Siliciumoxid fällt in einem pH-Bereich von 2-9, vorzugsweise 6-9 aus. Die weiteren aufgeführten Salze fallen in einem pH-Bereich zwischen 1(Bismuthoxinitrat) und 8 (Calciummolybdat) aus.Suitable acids are e.g. Phosphoric acid and acetic acid and especially nitric acid. Aqueous alkali hydroxide solutions or ammonia solutions, preferably aqueous sodium hydroxide solution, can expediently be used as bases. The pH is important for the coating so that the coating materials fail. In the case of phosphates, pH values between 5 and 10, preferably between 5 and 7, are expedient. For hydroxides, a pH range between 1 (bismuth hydroxide) and 11 (calcium and barium hydroxide) can be used; however, the preferred aluminum and zinc hydroxides are in the range 4 to 8. Most oxides or water-containing oxides are precipitated at pH values between 2 and 4. However, higher pH values up to 10 have no negative influence. Silicon oxide precipitates in a pH range of 2-9, preferably 6-9. The other salts listed fall out in a pH range between 1 (bismuth oxin nitrate) and 8 (calcium molybdate).
Die thermische Behandlung (c) (Calcinierung) wird nach üblichen Methoden vorzugsweise zwischen 100 und 600°C, besonders bevorzugt zwischen 300 und 450 °C und insbesondere bei 400°C durchgeführt.The thermal treatment (c) (calcination) is carried out by conventional methods, preferably between 100 and 600 ° C., particularly preferably between 300 and 450 ° C. and in particular at 400 ° C.
Nach der Calcinierung kann die Beschichtung, wenn für die vorgesehene Verwendung zweckmässig, durch Behandlung mit einer Säure oder Base entfernt werden und gegebenenfalls mit anderen üblichen Beschichtungs mitteln ersetzt werden, ohne Beeinträchtigung der Transparenz. Geeignete Säuren und Basen sind z.B. die gleichen, die oben bereits im Zusammenhang mit der pH-Einstellung erwähnt wurden.After the calcination, the coating can, if appropriate for the intended use, be removed by treatment with an acid or base and, if appropriate, replaced with other customary coating agents, without impairing the transparency. Suitable acids and bases are e.g. the same ones mentioned above in connection with pH adjustment.
Die durch das erfindungsgemässe Verfahren erhaltenen Produkte sind, wie bereits erwähnt, durch eine bei Bismuthvanadat-Pigmenten bisher nie erlangten Transparenz gekennzeichnet. Sie sind demnach neu und bilden einen weiteren Gegenstand der vorliegenden Anmeldung.As already mentioned, the products obtained by the process according to the invention are characterized by a transparency never previously achieved with bismuth vanadate pigments. They are therefore new and form a further subject of the present application.
Die Transparenz wird hier durch ΔL* gemäss CIELAB gekennzeichnet und zwar mit AL*>4, wobei
L* (weiss) bzw. L* (schwarz) werden durch Farbmessung einer Alkyd-Melamin Lack applikation bei einem Pigmentanteil (Festkörpergehalt) von 38 %, mit einer Schichtdicke (trocken) von 40 µm auf einem Schwarz-Weiss-Kontrastkarton und Berechnung nach der ClELAB-Formel (ISO 7724-1 bis 7724-3) ermittelt.L * (white) or L * (black) are measured by color measurement of an alkyd-melamine lacquer application with a pigment content (solids content) of 38%, with a layer thickness (dry) of 40 µm on a black and white contrast cardboard and calculation the ClELAB formula (ISO 7724-1 to 7724-3).
Die vorliegende Erfindung betrifft demnach auch Bismuth vanadat-Pigmente der allgemeinen Zusammensetzung
Bei den Metallen und Nichtmetallen, die Bismuth und Vanadium teilweise ersetzten können, handelt es sich vorzugsweise um Li, Mg, Zn, Al und insbesondere Ca, sowie W und insbesondere P und Mo.The metals and non-metals, which can partially replace bismuth and vanadium, are preferably Li, Mg, Zn, Al and in particular Ca, and W and in particular P and Mo.
Bevorzugt handelt es sich um Bismuthvanadat-Pigmente auf Basis der oben bereits erwähnten C.I. Pigment Yellow 184-Typen.Bismuth vanadate pigments based on the C.I. Pigment Yellow 184 types.
Die erfindungsgemässen transparenten Bismuthvanadate können als Pigmente für hochmolekulare organische Materialien verwendet werden.The transparent bismuth vanadates according to the invention can be used as pigments for high-molecular organic materials.
Hochmolekulare organische Materialien, die mit den erfindungsgemässen Bismuthvanadaten pigmentiert werden können, sind z.B. Cellulose ether und -ester, wie Ethylcellulose, Nitrocellulose, Celluloseacetat und Cellulosebutyrat, natürliche Harze und Kunstharze, wie Polymerisationsharze oder Kondensationsharze, z.B. Aminoplaste, insbesondere Harnstoff- und Melamin-Formaldehydharze, Alkydharze, Phenoplaste, Polycarbonate, Polyolefine, wie Polyethylen und Polypropylen, Polystyrol, Polyvinylchlorid, Polyacrylnitril, Polyacrylsäureester, Polyamide, Polyurethane, Polyester, Gummi, Casein, Silikon und Silikonharze, einzeln oder in Mischungen.High molecular weight organic materials which can be pigmented with the bismuth vanadates according to the invention are, for example, cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins and synthetic resins, such as polymerization resins or condensation resins, for example aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polyethylene and polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes, polyesters, rubbers, casein, silicone and silicone resins , individually or in mixtures.
Dabei spielt es keine Rolle, ob die erwähnten hochmolekularen organischen Verbindungen als plastische Massen, Schmelzen oder in Form von Spinnlösungen, Lacken, Anstrichstoffen oder Druckfarben vorliegen. Je nach Verwendungs zweck erweist es sich als vorteilhaft, die erfindungsgemässen Bismuth vanadate als Toner oder in Form von Präparaten einzusetzen. Bezogen auf das zu pigmentierende hochmolekulare organische Material kann man die erfindungsgemässen Bismuthvanadate in einer Menge von 0,01 bis 75 Gew.-%, vorzugsweise 0,1 bis 50 Gew.-%, einsetzen.It does not matter whether the high-molecular organic compounds mentioned are present as plastic masses, melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the intended use, it proves to be advantageous to use the bismuth vanadate according to the invention as a toner or in the form of preparations. Based on the high molecular weight organic material to be pigmented, the bismuth vanadates according to the invention can be used in an amount of 0.01 to 75% by weight, preferably 0.1 to 50% by weight.
Die erhaltenen Ausfärbungen, beispielsweise in Kunststoffen, Fasern, Lacken oder Drucken zeichnen sich, ausser durch die ausserordentlich hohe Farbton-Reinheit und Transparenz durch hohe Farbstärke, gute Dispergierbarkeit, gute Überlackier-, Migrations-, Hitze-, Licht- und Wetterbeständigkeit, sowie durch einen guten Glanz, aus.The colorations obtained, for example in plastics, fibers, paints or prints, are distinguished, in addition to the extraordinarily high color purity and transparency, by high color strength, good dispersibility, good resistance to overpainting, migration, heat, light and weather, and by a good shine from.
Die erfindungsgemässen Bismuthvanadate zeichnen sich aber, wie bereits erwähnt, ganz besonders durch ihre hohe Transparenz aus. Demnach eignen sie sich vorzugsweise zum Färben von Kunststoffen, Druck farben und wässrigen und/oder lösungsmittel haltigen Lacken, insbesondere Automobillacken. Ganz besonders bevorzugt ist ihre Verwendung für Metalleffektlackierungen (Metall oder Mica).However, as already mentioned, the bismuth vanadates according to the invention are particularly notable for their high transparency. Accordingly, they are preferably suitable for coloring plastics, printing inks and aqueous and / or solvent-based paints, in particular automotive paints. Their use is particularly preferred for metallic effect coatings (metal or mica).
Die nachfolgenden Beispiele dienen zur Erläuterung der Erfindung. Sofern nichts anderes vermerkt, bedeuten Prozente Gewichtsprozente.The following examples serve to explain the invention. Unless otherwise noted, percentages mean percentages by weight.
Beispiel 1: 98,4 g Bismuthnitratpentahydrat und 6,4 g Calciumnitrattetrahydrat werden unter Rühren in 74,4 g Salpetersäure (54%-ig) und 580 ml Wasser gelöst. Die erhaltene Lösung wird innerhalb von 3 Minuten unter intensivem Rühren mit einer Vanadat lösung, bestehend aus 35,4 g Natriumorthovanadat, 4,0 g Natriumhydroxid und 6,6 g Natriummolybdatdihydrat in 600 ml Wasser, versetzt. Der pH der entstandenen Suspension wird inner halb von einigen Minuten durch Zugabe von 20 %-iger Natronlauge auf einen Wert von 3,5 angehoben. Nach einer Rührzeit von 60 Minuten erhöht man durch Zugabe von 1 molarer Natronlauge den pH der Suspension innerhalb von 20 Minuten auf einen Wert von 6,5 und lässt weitere 30 Minuten rühren. Zu dieser Suspension gibt man in 20 Minuten eine Lösung aus 39,0 g Phosphorsäure (75%-ig), 53,0 g Aluminiumsulfathydrat und 44,0 g Zinksulfatheptahydrat aufgelöst in 300 ml Wasser, worauf der pH-Wert sinkt. Wird ein p H-Wert von 2,0 unterschritten, wird 20%-ige Natronlauge zudosiert. Der pH der Suspension wird dann in 60 Minuten mit 1 molarer Natronlauge auf einen Wert von 6,5 eingestellt und weitere 30 Minuten gerührt. Nach Filtration, zweimaligem Waschen mit 500 ml Wasser und trocknen bei 100°C wird der erhaltene Feststoff 20 Stunden bei 400°C geglüht. Nach Abkühlen des Glühproduktes wird es in einer Pulver-Mühle desagglomeriert. Example 1 : 98.4 g of bismuth nitrate pentahydrate and 6.4 g of calcium nitrate tetrahydrate are dissolved with stirring in 74.4 g of nitric acid (54%) and 580 ml of water. The solution obtained is mixed with a vanadate solution consisting of 35.4 g of sodium orthovanadate, 4.0 g of sodium hydroxide and 6.6 g of sodium molybdate dihydrate in 600 ml of water within 3 minutes with vigorous stirring. The pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution raised. After a stirring time of 60 minutes, the pH of the suspension is increased to a value of 6.5 within 20 minutes by adding 1 molar sodium hydroxide solution and stirring is continued for a further 30 minutes. A solution of 39.0 g of phosphoric acid (75%), 53.0 g of aluminum sulfate hydrate and 44.0 g of zinc sulfate heptahydrate dissolved in 300 ml of water is added to this suspension in 20 minutes, whereupon the pH drops. If the pH falls below 2.0, 20% sodium hydroxide solution is added. The pH of the suspension is then adjusted to a value of 6.5 in 1 minute with 1 molar sodium hydroxide solution and stirred for a further 30 minutes. After filtration, washing twice with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 20 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
Das erhaltene Pigment wird in einem AM-Lack nach folgender Vorgehensweise appliziert:The pigment obtained is applied in an AM lacquer according to the following procedure:
37,0 g eines Alkydmelamin-Lackes der folgenden Zusammensetzung
- 18,7 g eines kurzkettigen Alkydharzes (Setal® 84xx70 (70 %) der Firma Synthese)
- 7,2 g eines Melaminharzes (Setamin® US 132 BB70 (70%) der Firma Synthese)
- 7,8 g Solvesso® 100 (aromatische Kohlenwasserstoffe; Esso)
- 1,7 g Butanol
- 0,8 g Depanol J (Terpen-Kohlenwasserstoff)
- 0,8 g Isophoron
- 18.7 g of a short-chain alkyd resin (Setal® 84xx70 (70%) from synthesis)
- 7.2 g of a melamine resin (Setamin® US 132 BB70 (70%) from synthesis)
- 7.8 g Solvesso® 100 (aromatic hydrocarbons; Esso)
- 1.7 g butanol
- 0.8 g Depanol J (terpene hydrocarbon)
- 0.8 g isophorone
Der Lack wird auf einem Kontrastkarton ausgezogen (Nassfilmdicke 75 µm), 20 Minuten abgelüftet und während 30 Minuten bei 130°C eingebrannt.The paint is drawn out on a contrasting cardboard (wet film thickness 75 µm), flashed off for 20 minutes and baked at 130 ° C for 30 minutes.
Farbmessungen nach der ClELAB-Methode (ISO 7724-1 bis 7724-3) ergeben folgende Werte: ΔL* = 11,2; ΔE* = 25,0Color measurements according to the ClELAB method (ISO 7724-1 to 7724-3) give the following values: ΔL * = 11.2; ΔE * = 25.0
Beispiel 2: 98,4 g Bismuthnitratpentahydrat und 6,4 g Calciumnitrattetrahydrat werden unter Rühren in 74,4 g Salpetersäure (54%-ig) und 580 ml Wasser gelöst. Die erhaltene Lösung wird innerhalb von 3 Minuten unter intensivem Rühren mit einer Vanadat lösung, bestehend aus 35,4 g Natriumorthovanadat, 4,0 g Natriumhydroxid und 6,6 g Natriummolybdatdihydrat in 600 ml Wasser, versetzt. Der pH der entstandenen Suspension wird innerhalb von einigen Minuten durch Zugabe von 20 %-iger Natronlauge auf einen Wert von 3,5 angehoben. Nach einer Rührzeit von 60 Minuten erhöht man durch Zugabe von 1 molarer Natronlauge den pH der Suspensi on innerhalb von 20 Minuten auf einen Wert von 6,5 und lässt weitere 30 Minuten rühren. Zu dieser Suspension gibt man in 5 Minuten eine Lösung aus 9,8 g Phosphorsäure (75%-ig), 13,3 g Aluminiumsulfathydrat und 11,0 g Zinksulfatheptahydrat aufgelöst in 300 ml Wasser, worauf sich ein pH-Wert von 1,2 ein stellt. Der pH der Suspension wird dann in 90 Minuten mit 1 molarer Natronlauge auf einen Wert von 6,5 eingestellt und weitere 30 Minuten gerührt. Nach Filtration, einmaligem Waschen mit 500 ml Wasser und trocknen bei 100 °C wird der erhaltene Feststoff 20 Stunden bei 400°C geglüht. Nach Abkühlen des Glühproduktes wird es in einer Pulver-Mühle desagglomeriert. Example 2: 98.4 g of bismuth nitrate pentahydrate and 6.4 g of calcium nitrate tetrahydrate are dissolved with stirring in 74.4 g of nitric acid (54%) and 580 ml of water. The solution obtained is mixed with a vanadate solution consisting of 35.4 g of sodium orthovanadate, 4.0 g of sodium hydroxide and 6.6 g of sodium molybdate dihydrate in 600 ml of water within 3 minutes with vigorous stirring. The pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution. After a stirring time of 60 minutes, the pH of the suspension is increased to 6.5 within 20 minutes by adding 1 molar sodium hydroxide solution and the mixture is stirred for a further 30 minutes. A solution of 9.8 g of phosphoric acid (75%), 13.3 g of aluminum sulfate hydrate and 11.0 g of zinc sulfate heptahydrate dissolved in 300 ml of water is added to this suspension in 5 minutes, after which a pH of 1.2 one poses. The pH of the suspension is then adjusted to a value of 6.5 in 1 minute with 1 molar sodium hydroxide solution and stirred for a further 30 minutes. After filtration, washing once with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 20 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
Das erhaltene Pigment wird, wie in Beispiel 1 beschrieben, in einem AM-Lack appliziert und einer Farbmessung unterzogen. Man erhält folgende Werte: ΔL* = 8,1; ΔE* = 19,7.As described in Example 1, the pigment obtained is applied in an AM lacquer and subjected to a color measurement. The following values are obtained: ΔL * = 8.1; ΔE * = 19.7.
Beispiel 3: 239,0 g Bismuthnitratpentahydrat und 12,8 g Calciumnitrattetrahydrat werden unter Rühren in 140,0 g Salpetersäure (54%-ig) und 1150,0 ml Wasser gelöst. Die erhaltene Lösung wird innerhalb von 1 Minute unter intensivem Rühren mit einer Vanadatlösung, bestehend aus 70,8 g Natriumorthovanadat, 7,9 g Natriumhydroxid und 13,2 g Natriummolybdatdihydrat in 700 ml Wasser, versetzt. Der pH der entstandenen Suspension wird innerhalb von einigen Minuten durch Zugabe von 20 %-iger Natronlauge auf einen Wert von 3,5 angehoben. Nach einer Rührzeit von 60 Minuten erhöht man durch Zugabe von 1 molarer Natronlauge den pH der Suspension innerhalb von 20 Minuten auf einen Wert von 6,5 und lässt weitere 30 Minuten rühren. Zu dieser Suspension gibt man in 5 Minuten eine Lösung aus 39,0 g Phosphorsäure (75%-ig), 53,0 g Aluminiumsulfathydrat und 44,0 g Zinksulfatheptahydrat aufgelöst in 200 ml Wasser, worauf sich ein pH-Wert von 1,0 einstellt. Der pH der Suspension wird dann in 10 Minuten mit 50%-iger Natronlauge auf einen Wert von 6,5 eingestellt und weitere 30 Minuten gerührt. Nach Filtration, einmaligem Waschen mit 500 ml Wasser und trocknen bei 100 °C wird der erhaltene Feststoff 16 Stunden bei 400°C geglüht. Nach Abkühlen des Glühproduktes wird es in 2 l Wasser erneut angeschlämmt und mittels einem Hochgeschwindigkeitsrührer 10 Minuten desagglomeriert. Zu dieser Suspension gibt man in 5 Minuten eine Lösung aus 35,0 g Phosphorsäure (75%-ig), 53,0 g Aluminiumsulfathydrat und 44,0 g Zinksulfatheptahydrat aufgelöst in 1200 ml Wasser worauf sich ein pH-Wert von 2,0 einstellt. Der pH der Suspension wird dann in 10 Minuten mit 20%-iger Natronlauge auf einen Wert von 6,5 eingestellt und weitere 30 Minuten gerührt. Nach Filtration, einmaligem Waschen mit 500 ml Wasser und trocknen bei 100 °C wird der erhaltene Feststoff 16 Stunden bei 400 °C geglüht. Nach Abkühlen des Glühproduktes wird es in einer Pulver-Mühle desagglomeriert. Example 3: 239.0 g bismuth nitrate pentahydrate and 12.8 g calcium nitrate tetrahydrate are dissolved with stirring in 140.0 g nitric acid (54%) and 1150.0 ml water. A vanadate solution consisting of 70.8 g of sodium orthovanadate, 7.9 g of sodium hydroxide and 13.2 g of sodium molybdate dihydrate in 700 ml of water is added to the resulting solution within 1 minute with vigorous stirring. The pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution. After a stirring time of 60 minutes, the pH of the suspension is increased to a value of 6.5 within 20 minutes by adding 1 molar sodium hydroxide solution and stirring is continued for a further 30 minutes. A solution of 39.0 g of phosphoric acid (75%), 53.0 g of aluminum sulfate hydrate and 44.0 g of zinc sulfate heptahydrate dissolved in 200 ml of water is added to this suspension in 5 minutes, after which the pH is 1.0 sets. The pH of the suspension is then adjusted to a value of 6.5 in 50 minutes with 50% sodium hydroxide solution and stirred for a further 30 minutes. After filtration, once Wash with 500 ml of water and dry at 100 ° C, the solid obtained is calcined at 400 ° C for 16 hours. After the glow product has cooled, it is reslurried in 2 l of water and deagglomerated for 10 minutes using a high-speed stirrer. A solution of 35.0 g of phosphoric acid (75%), 53.0 g of aluminum sulfate hydrate and 44.0 g of zinc sulfate heptahydrate dissolved in 1200 ml of water is added to this suspension in 5 minutes, after which a pH of 2.0 is established . The pH of the suspension is then adjusted to a value of 6.5 in 20 minutes with 20% sodium hydroxide solution and stirred for a further 30 minutes. After filtration, washing once with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 16 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
Das erhaltene Pigment wird, wie in Beispiel 1 beschrieben, in einem AM-Lack appliziert und einer Farbmessung unterzogen. Man erhält folgende Werte: ΔL* = 9,2; ΔE* = 20,7.As described in Example 1, the pigment obtained is applied in an AM lacquer and subjected to a color measurement. The following values are obtained: ΔL * = 9.2; ΔE * = 20.7.
Beispiel 4: 98,4 g Bismuthnitratpentahydrat und 6,4 g Calciumnitrattetrahydrat werden unter Rühren in 74,4 g Salpetersäure (54%-ig) und 580 ml Wasser gelöst. Die erhaltene Lösung wird innerhalb von 3 Minuten unter intensivem Rühren mit einer Vanadat iösung, bestehend aus 35,4 g Natriumorthovanadat, 4,0 g Natriumhydroxid und 6,6 g Natriummolybdatdihydrat in 600 ml Wasser, versetzt. Der pH der entstandenen Suspension wird innerhalb von einigen Minuten durch Zugabe von 20 %-iger Natronlauge auf einen Wert von 3,5 angehoben. Nach einer Rührzeit von 30 Minuten erhöht man durch Zugabe von 20%-iger Natronlauge den pH der Suspension innerhalb von 60 Minuten auf einen Wert von 6,5 und lässt weitere 30 Minuten rühren. Zu dieser Suspension gibt man in 10 Minuten eine Lösung aus 53,0 g Aluminiumsulfathydrat und 44,0 g Zinksulfatheptahydrat aufgelöst in 600 ml Wasser, worauf sich ein pH-Wert von 3,1 ein stellt. Der pH der Suspension wird dann in 120 Minuten mit 1 molarer Natronlauge auf einen Wert von 6,5 eingestellt und weitere 30 Minuten gerührt. Nach Filtration, dreimaligem Waschen mit 500 ml Wasser und trocknen bei 100°C wird der erhaltene Feststoff 24 Stunden bei 400°C geglüht. Nach Abkühlen des Glühproduktes wird es in einer Pulver-Mühle desagglomeriert. Example 4: 98.4 g of bismuth nitrate pentahydrate and 6.4 g of calcium nitrate tetrahydrate are dissolved with stirring in 74.4 g of nitric acid (54%) and 580 ml of water. A vanadate solution consisting of 35.4 g of sodium orthovanadate, 4.0 g of sodium hydroxide and 6.6 g of sodium molybdate dihydrate in 600 ml of water is added to the resulting solution within 3 minutes with vigorous stirring. The pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution. After a stirring time of 30 minutes, the pH of the suspension is increased to 6.5 within 60 minutes by adding 20% sodium hydroxide solution and the mixture is left to stir for a further 30 minutes. A solution of 53.0 g of aluminum sulfate hydrate and 44.0 g of zinc sulfate heptahydrate dissolved in 600 ml of water is added to this suspension in 10 minutes, after which a pH of 3.1 is established. The pH of the suspension is then adjusted to a value of 6.5 in 1 minute with 1 molar sodium hydroxide solution and stirred for a further 30 minutes. After filtration, washing three times with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 24 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
Das erhaltene Pigment wird, wie in Beispiel 1 beschrieben, in einem AM-Lack appliziert und einer Farbmessung unterzogen. Man erhält folgende Werte: ΔL* = 6,0, ΔE* = 15,2.As described in Example 1, the pigment obtained is applied in an AM lacquer and subjected to a color measurement. The following values are obtained: ΔL * = 6.0, ΔE * = 15.2.
Beispiel 5: 123,6 g Bismuthnitratpentahydrat werden unter Rühren in 53,0 g Salpetersäure (54%-ig) und 570 ml Wasser gelöst. Die erhaltene Lösung wird innerhalb von 3 Minuten unter intensivem Rühren mit einer Vanadat lösung, bestehend aus 48,9 g Natriumorthovanadat, 5,5 g Natriumhydroxid in 600 ml Wasser, versetzt. Der pH der entstandenen Suspension wird innerhalb von einigen Minuten durch Zugabe von 20 %-iger Natronlauge auf einen Wert von 3,5 angehoben. Nach einer Rührzeit von 30 Minuten erhöht man durch Zugabe von 20%-iger Natronlauge den pH der Suspension innerhalb von 60 Minuten auf einen Wert von 6,5 und lässt weitere 16 Stunden rühren. Zu dieser Suspension gibt man 1 g Natriumhexamethaphosphat und dispergiert 6 Minuten mittels eines Hochgeschwindigkeitsrührers. Nach der Dispergierung gibt man zu dieser Suspension in 10 Minuten eine Lösung aus 66,5 g Aluminiumsulfathydrat und 55,0 g Zinksulfatheptahydrat und 49,0 g Phosphorsäure (75%-ig) aufgelöst in 600 ml Wasser, worauf sich ein pH-Wert von 1,9 einstellt Der pH der Suspension wird dann in 30 Minuten mit 20%-iger Natronlauge auf einen Wert von 6,5 eingestellt und weitere 30 Minuten gerührt. Nach Filtration, zweimaligem waschen mit 500 ml Wasser und trocknen bei 100 °C wird der erhaltene Feststoff 24 Stunden bei 400 °C geglüht. Nach Abkühlen des Glühproduktes wird es in einer Pulver-Mühle desagglomeriert. 50 g des erhaltenen Pigments werden in 2,0 l Wasser und 5,0 g Natriumhexametaphosphat 20 Minuten bei 100°C mittels eines Hochgeschwindigkeitsrührers redispergiert. Zu der erhaltenen Suspension gibt man in 10 Minuten eine Lösung aus 7,6 g Cerium(lll)-chlorid in 250 ml Wasser worauf sich ein pH von 4,1 einstellt. Der pH der Suspension wird in 15 Minuten mit 1 molarer Natronlauge auf einen Wert von 10,0 erhöht und lässt 30 Minuten weiter rühren. Nach Filtration, zweimaligem Waschen mit 500 ml Wasser und trocknen bei 100 °C wird der erhaltene Feststoff 16 Stunden bei 400°C geglüht Nach Abkühlen des Glühproduktes wird es in einer Pulver-Mühle desagglomeriert. Example 5: 123.6 g of bismuth nitrate pentahydrate are dissolved with stirring in 53.0 g of nitric acid (54%) and 570 ml of water. The solution obtained is mixed with a vanadate solution consisting of 48.9 g of sodium orthovanadate, 5.5 g of sodium hydroxide in 600 ml of water within 3 minutes with vigorous stirring. The pH of the resulting suspension is raised to a value of 3.5 within a few minutes by adding 20% sodium hydroxide solution. After a stirring time of 30 minutes, the pH of the suspension is increased to 6.5 within 60 minutes by adding 20% sodium hydroxide solution and the mixture is stirred for a further 16 hours. 1 g of sodium hexamethaphosphate is added to this suspension and dispersed for 6 minutes using a high-speed stirrer. After the dispersion, a solution of 66.5 g of aluminum sulfate hydrate and 55.0 g of zinc sulfate heptahydrate and 49.0 g of phosphoric acid (75% strength) dissolved in 600 ml of water is added to this suspension in 10 minutes, which results in a pH of The pH of the suspension is then adjusted to 6.5 in 20 minutes with 20% sodium hydroxide solution and the mixture is stirred for a further 30 minutes. After filtration, washing twice with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 24 hours. After the annealing product has cooled, it is deagglomerated in a powder mill. 50 g of the pigment obtained are redispersed in 2.0 l of water and 5.0 g of sodium hexametaphosphate for 20 minutes at 100 ° C. using a high-speed stirrer. A solution of 7.6 g of cerium (III) chloride in 250 ml of water is added to the suspension obtained in 10 minutes, after which a pH of 4.1 is established. The pH of the suspension is raised to a value of 10.0 with 1 molar sodium hydroxide solution in 15 minutes and stirring is continued for 30 minutes. After filtration, washing twice with 500 ml of water and drying at 100 ° C., the solid obtained is calcined at 400 ° C. for 16 hours. After the annealing product has cooled, it is deagglomerated in a powder mill.
Das erhaltene Pigment wird, wie in Beispiel 1 beschrieben, in einem AM-Lack appliziert und einer Farbmessung unterzogen. Man erhält folgende Werte: ΔL* = 7,9; ΔE* = 19,5.As described in Example 1, the pigment obtained is applied in an AM lacquer and subjected to a color measurement. The following values are obtained: ΔL * = 7.9; ΔE * = 19.5.
Claims (12)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH137096 | 1996-05-31 | ||
| CH1370/96 | 1996-05-31 | ||
| CH137096 | 1996-05-31 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0810269A2 true EP0810269A2 (en) | 1997-12-03 |
| EP0810269A3 EP0810269A3 (en) | 1998-07-22 |
| EP0810269B1 EP0810269B1 (en) | 2003-09-03 |
Family
ID=4208833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19970810315 Expired - Lifetime EP0810269B1 (en) | 1996-05-31 | 1997-05-22 | Transparent bismuth vanadate pigments |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5853472A (en) |
| EP (1) | EP0810269B1 (en) |
| JP (1) | JPH10101338A (en) |
| KR (1) | KR100499596B1 (en) |
| DE (1) | DE59710675D1 (en) |
| TW (1) | TW373006B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000020515A1 (en) * | 1998-10-01 | 2000-04-13 | Ciba Specialty Chemicals Holding Inc. | Red-tinged bismuth vanadate pigments |
| EP3024896A4 (en) * | 2013-07-25 | 2017-02-15 | Basf Se | Bismuth vanadate pigments |
| CN113877632A (en) * | 2021-11-16 | 2022-01-04 | 江西省科学院应用化学研究所 | Preparation method of 2D bismuth vanadate @ PDA core-shell structure composite material loaded with noble metal nanoparticles |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19840156A1 (en) * | 1998-09-03 | 2000-03-09 | Basf Ag | Bismuth vanadate pigments with at least one coating containing metal fluoride |
| DE19934206A1 (en) * | 1999-07-21 | 2001-01-25 | Basf Ag | Pigment preparations containing phosphate |
| JP5444232B2 (en) * | 2007-10-18 | 2014-03-19 | ラバー ナノ プロダクツ （プロプライエタリー） リミテッド | Production of coating materials for use as activators in sulfur vulcanization. |
| JP5251809B2 (en) * | 2009-09-25 | 2013-07-31 | 東洋インキＳｃホールディングス株式会社 | Aqueous dispersion and water-based coating composition having solar heat shielding effect |
| CN105838111B (en) * | 2016-05-25 | 2018-02-23 | 赣州有色冶金研究所 | Pearlescent pigment with heat discoloration effect and preparation method thereof and system |
| JP7098992B2 (en) * | 2018-03-20 | 2022-07-12 | セイコーエプソン株式会社 | Inkjet ink set |
| CN115043427B (en) * | 2022-07-28 | 2023-07-04 | 中南大学 | High-concentration colloidal antimony pentoxide and preparation method thereof |
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| US4063956A (en) * | 1976-09-16 | 1977-12-20 | E. I. Du Pont De Nemours And Company | Heat stable monoclinic bismuth vanadate pigment |
| EP0074049A2 (en) * | 1981-09-05 | 1983-03-16 | BASF Aktiengesellschaft | Pigment containing yellow bismuth vanadate and process for manufacturing the same |
| EP0239526A2 (en) * | 1986-02-19 | 1987-09-30 | Ciba-Geigy Ag | Inorganic compounds based on bismuth vanadate |
| EP0430888A1 (en) * | 1989-11-30 | 1991-06-05 | Ciba-Geigy Ag | Process for preparing bismuth vanadate pigments and bismuth vanadate pigments of high tinting strength |
| GB2238549A (en) * | 1989-11-30 | 1991-06-05 | Ciba Geigy Ag | Process for stabilising bismuth vanadate pigments against attack by hydrochloric acid |
| EP0640566A1 (en) * | 1993-08-24 | 1995-03-01 | BASF Lacke + Farben AG | Bismuth vanadate pigments |
| EP0723998A1 (en) * | 1995-01-25 | 1996-07-31 | Bayer Ag | Colour-fast yellow bismuth vanadate pigment |
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| US3843554A (en) * | 1970-09-24 | 1974-10-22 | Du Pont | Catalyst compositions of scheelite crystal structure containing vanadium,bismuth and cation vacancies |
| DE2402694A1 (en) * | 1974-01-21 | 1975-07-24 | Hoechst Ag | A PROCESS FOR THE PRODUCTION OF EASILY DISPERSIBLE AND GRIP STABLE MOLYBDATROTCHROME YELLOW PIGMENTS |
| US4115142A (en) * | 1976-06-22 | 1978-09-19 | E. I. Du Pont De Nemours And Company | Pigmentary bright primrose yellow monoclinic bismuth vanadate and processes for the preparation thereof |
| IT1110668B (en) * | 1979-02-09 | 1985-12-23 | Montedison Spa | NEW INORGANIC PIGMENTS AND PROCESS TO PREPARE THEM |
| IT1195261B (en) * | 1980-02-25 | 1988-10-12 | Montedison Spa | NEW INORGANIC PIGMENTS AND PROCESS TO PREPARE THEM |
| EP0441101A1 (en) * | 1990-01-11 | 1991-08-14 | Ciba-Geigy Ag | Phosphate modified bismuth vanadate pigments |
| DE4040849A1 (en) * | 1990-12-20 | 1992-06-25 | Bayer Ag | Bismuth Vanadate pigments, process for their preparation and their use |
| US5336312A (en) * | 1991-04-24 | 1994-08-09 | Ferro Corporation | Bismuth-containing colorants |
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- 1997-05-22 EP EP19970810315 patent/EP0810269B1/en not_active Expired - Lifetime
- 1997-05-22 DE DE59710675T patent/DE59710675D1/en not_active Expired - Lifetime
- 1997-05-27 US US08/863,312 patent/US5853472A/en not_active Expired - Lifetime
- 1997-05-29 TW TW086107298A patent/TW373006B/en active
- 1997-05-30 KR KR1019970021997A patent/KR100499596B1/en active IP Right Grant
- 1997-05-30 JP JP14079197A patent/JPH10101338A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000020515A1 (en) * | 1998-10-01 | 2000-04-13 | Ciba Specialty Chemicals Holding Inc. | Red-tinged bismuth vanadate pigments |
| US6444025B1 (en) | 1998-10-01 | 2002-09-03 | Ciba Specialty Chemicals Corporation | Red-tinged bismuth vanadate pigments |
| EP3024896A4 (en) * | 2013-07-25 | 2017-02-15 | Basf Se | Bismuth vanadate pigments |
| US9868860B2 (en) | 2013-07-25 | 2018-01-16 | Basf Se | Bismuth vanadate pigments |
| CN113877632A (en) * | 2021-11-16 | 2022-01-04 | 江西省科学院应用化学研究所 | Preparation method of 2D bismuth vanadate @ PDA core-shell structure composite material loaded with noble metal nanoparticles |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0810269B1 (en) | 2003-09-03 |
| KR970074871A (en) | 1997-12-10 |
| US5853472A (en) | 1998-12-29 |
| DE59710675D1 (en) | 2003-10-09 |
| JPH10101338A (en) | 1998-04-21 |
| EP0810269A3 (en) | 1998-07-22 |
| TW373006B (en) | 1999-11-01 |
| KR100499596B1 (en) | 2005-09-08 |
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